Thioepoxy based polymerizable composition and method for production thereof

ABSTRACT

A polymerizable composition and a manufacturing method thereof are provided, in which the composition is capable of meeting requirements of overcoming decrease in production yield of a resin composed of a thioepoxy compound, the decrease being caused by variations in refractive index, hue, and optical strain. 
                         
In a polymerizable composition containing a compound having at least one structure represented by the above formula (where R 1  represents a hydrocarbon having 1 to 10 carbon atoms, R 2 , R 3 , and R 4  each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.), the total of a thioepoxy compound A, which has at least one structure represented by formula (2) and at least one structure represented by formula (3), and a thioepoxy compound B, which has at least one structure represented by formula (4) and at least one structure represented by formula (3), is 4 mass percent or less with respect to the total mass of the polymerizable composition.

TECHNICAL FIELD

The present invention relates to thioepoxy compounds and cured resinsobtained therefrom, which thioepoxy compounds are preferably used inresin fields of optical materials or the like which are required to havea high refractive index and high transparence.

BACKGROUND ART

Since being lighter and less brittle than inorganic lenses, and beingdyeable, in recent years, plastic lenses have been increasingly indemands for optical elements such as glass lenses and camera lenses.

Among properties which have been required for those plastic lenses, ahigh refractive index and a high Abbe number are required as opticalproperties, and high heat resistance and low specific gravity arerequired as physical properties.

At present, as a resin which has satisfied those requirements mentionedabove to some extent, for example, a polythiourethane resin whichcontains sulfur atoms therein has been known. Since having a highrefractive index, superior impact resistance, and the like, thepolythiourethane resin has been regarded as a well-balanced resin (forexample, referred to Japanese Unexamined Patent Application PublicationNo. 63-46213).

However, although a higher refractive index and a higher Abbe numberhave been further required, it has been very difficult to improve theabove two requirements at the same time since in the relationshipbetween the two properties described above, as the refractive index isincreased, the Abbe number is decreased. Hence, researches have beenaggressively carried out so that the refractive index is increased whilethe decrease in Abbe number is suppressed.

Among the researches mentioned above, a method using a thioepoxycompound may be a typical proposal (for example, referred to WO-89/10575and Japanese Unexamined Patent Application Publication No. 9-110979).

According to the methods mentioned above, while having a relatively highAbbe number, the resin is able to have a high refractive index. However,due to variation in quality of polymerizable compounds used as a rawmaterial, which occurs in industrial manufacturing thereof, resinsformed by the methods described above may have unstable refractiveindexes or hues in some cases, and in addition, optical strain may beliable to be generated in some cases. In the case in which therefractive index varies, a problem may arise in that when a resin isused for a lens, power of lens may vary. In the case in which the huevaries, a problem may arise in that when a resin is used for glasslenses, a pair of lenses may be formed which have different colors fromeach other. Among resins used for optical applications, a resin havingoptical strain is rejected as a defective product. Accordingly, whenoptical strain becomes liable to be generated, the production yield ofthe resin is significantly decreased, resulting in industrialdisadvantages. Hence, reasons causing the variations in refractiveindex, hue, and optical strain must have been clearly understood.

DISCLOSURE OF INVENTION

In order to solve the problems described above, through intensiveresearch carried out by the inventors of the present invention oncompounds which are by-produced when a thioepoxy compound ismanufactured, the behavior of the compounds could be successfullygrasped. That is, it was found that a thioepoxy compound A, which has atleast one structure represented by formula (2) and at least onestructure represented by formula (3), and a thioepoxy compound B, whichhas at least one structure represented by formula (4) and at least onestructure represented by formula (3), cause the variation in refractiveindex, hue, and optical strain of a resin. In addition, as for theacceptable amount of the compounds described above, it was also found atthe same time that when the total amount of the thioepoxy compound A andthe thioepoxy compound B is 0 with respect to the total mass of apolymerizable composition, no problems occur at all, and that when thetotal amount is 4 mass percent or less, the refractive index and the hueof an obtained resin are stabilized and the optical strain is unlikelyto be generated.

In addition, as for a polymerizable composition having at least onestructure represented by formula (1) according to the present invention,an industrial manufacturing method have been studied so that the totalof the thioepoxy compound A and the thioepoxy compound B is 4 masspercent or less with respect to the total mass of the polymerizablecomposition. As a result, it was found that when purification isperformed by column chromatography using a silica gel column or thelike, the total of the thioepoxy compound A and the thioepoxy compound Bcontained in an obtained polymerizable composition can be decreased;however, this can only be performed experimentally, and from anindustrial point of view, separation performed by chromatography is notpreferable in terms of cost and efficiency. Hence, study primarilyfocused on an industrially available manufacturing method has beenfurther carried out by the inventors. As a result, it was found that bythe following manufacturing methods or by the combination thereof, anindustrial method for manufacturing a polymerizable composition can beobtained in which the total of the thioepoxy compound A and thethioepoxy compound B is 4 mass percent or less with respect to the totalmass of the polymerizable composition, and hence the present inventionwas made. As the above manufacturing methods, for example, there may bementioned a method in which the amount of a thiation agent, which isused in forming a compound having at least one structure represented byformula (1), is limited, that is, the amount of a thiation agent usedfor forming a known polythioepoxy compound is set in the range of from0.9 to 1.3 equivalents with respect to one epoxy equivalent of thepolythioepoxy compound; a method in which the amount of an acid or theanhydride thereof is limited, that is, the amount of an acid or theanhydride thereof is set to 0.2 equivalents or less with respect to oneepoxy equivalent of the polythioepoxy compound; and in addition, amethod in which the reaction temperature is controlled in the range offrom 0° C. to 50° C.

That is, the present invention is as follows.

-   [1] In a polymerizable composition which comprises a compound having    at least one structure represented by formula (1):

(Where R₁ represents a hydrocarbon having 1 to 10 carbon atoms, R₂, R₃,and R₄ each represent a hydrocarbon group having 1 to 10 carbon atoms ora hydrogen atom.), the total of a thioepoxy compound A, which has atleast one structure represented by formula (2) and at least onestructure represented by formula (3), and a thioepoxy compound B, whichhas at least one structure represented by formula (4) and at least onestructure represented by formula (3), is 4 mass percent or less withrespect to the total mass of the polymerizable composition.

-   [2] In the polymerizable composition described in [1], the thioepoxy    compound A is a compound represented by formula (5), the thioepoxy    compound B is a compound represented by formula (6), and the    compound having at least one structure represented by formula (1) is    a compound represented by formula (7).

(where Y represents a substituted or unsubstituted, linear, branched, orcyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,a substituted or unsubstituted 1,4-dithiane group, an arylene group, oran aralkylene group. m represents an integer of 0 to 2, and n representsan integer of 0 to 4.)

(where R₅ to R₁₀ each represent a hydrocarbon group having 1 to 10carbon atoms or hydrogen. Y represents a substituted or unsubstituted,linear, branched, or cyclic divalent hydrocarbon group having 1 to 10carbon atoms, a substituted or unsubstituted 1,4-dithiane group, anarylene group, or an aralkylene group. m represents an integer of 0 to2, and n represents an integer of 0 to 4.)

-   [3] In the polymerizable composition described in [1] or [2], the    thioepoxy compound A comprises    2,3-epidithiopropyl(2,3-epithiopropyl)disulfide and/or    2,3-epidithiopropyl(2,3-epithiopropyl)sulfide, the thioepoxy    compound B comprises 2,3-epoxypropyl(2,3-epithiopropyl)disulfide    and/or 2,3-epoxypropyl(2,3-epithiopropyl)sulfide, and the compound    having at least one structure represented by formula (1) comprises    bis(2,3-epithiopropyl)disulfide and/or    bis(2,3-epithiopropyl)sulfide.-   [4] A method for manufacturing a polymerizable composition,    comprises forming a polythioepoxy compound from a polyepoxy    compound, wherein a thiation agent in an amount of 0.9 to 1.3    equivalents is used with respect to one epoxy equivalent of the    polyepoxy compound so that the total of a thioepoxy compound A and a    thioepoxy compound B, which are in formula (1), is 4 mass percent or    less with respect to the total mass of the polymerizable    composition.-   [5] A method for manufacturing a polymerizable composition,    comprises forming a polythioepoxy compound from a polyepoxy    compound, wherein a thiation agent in an amount of 0.9 to 1.3    equivalents is used with respect to one epoxy equivalent of the    polyepoxy compound, and the reaction temperature is set to 0° C. to    50° C. so that the total of a thioepoxy compound A and a thioepoxy    compound B, which are in formula (1), is 4 mass percent or less with    respect to the total mass of the polymerizable composition.-   [6] A method for manufacturing a polymerizable composition,    comprises forming a polythioepoxy compound from a polyepoxy    compound, wherein a thiation agent in an amount of 0.9 to 1.3    equivalents is used with respect to one epoxy equivalent of the    polyepoxy compound, an acid or the anhydride thereof in an amount of    0.2 equivalents or less is used with respect to one epoxy equivalent    of the polyepoxy compound, and the reaction temperature is set to    0° C. to 50° C. so that the total of a thioepoxy compound A and a    thioepoxy compound B, which are in formula (1), is 4 mass percent or    less with respect to the total mass of the polymerizable    composition.-   [7] In the manufacturing method described in one of [4] to [6], the    thioepoxy compound A is a compound represented by formula (5), the    thioepoxy compound B is a compound represented by formula (6), and a    compound having at least one structure represented by formula (1) is    a compound represented by formula (7).

(where Y represents a substituted or unsubstituted, linear, branched, orcyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,a substituted or unsubstituted 1,4-dithiane group, an arylene group, oran aralkylene group. m represents an integer of 0 to 2, and n representsan integer of 0 to 4.)

(where R₅ to R₁₀ each represent a hydrocarbon group having 1 to 10carbon atoms or hydrogen. Y represents a substituted or unsubstituted,linear, branched, or cyclic divalent hydrocarbon group having 1 to 10carbon atoms, a substituted or unsubstituted 1,4-dithiane group, anarylene group, or an aralkylene group. m represents an integer of 0 to2, and n represents an integer of 0 to 4.)

-   [8] In the manufacturing method described in [7], the thioepoxy    compound A comprises 2,3-epidithiopropyl(2,3-epithiopropyl)disulfide    and/or 2,3-epidithiopropyl(2,3-epithiopropyl)sulfide, the thioepoxy    compound B comprises 2,3-epoxypropyl(2,3-epithiopropyl)disulfide    and/or 2,3-epoxypropyl(2,3-epithiopropyl)sulfide, and the compound    having at least one structure represented by formula (1) comprises    bis(2,3-epithiopropyl)disulfide and/or    bis(2,3-epithiopropyl)sulfide.-   [9] A method for manufacturing an optical material, wherein the    optical material is obtained using the polymerizable composition    described in one of [1] to [3] and/or the polymerizable composition    obtained by the method described in one of [4] to [8].-   [10] In the manufacturing method described in [9], the optical    material comprises a lens.-   [11] In the manufacturing method described in [10], cast    polymerization is performed.-   [12] A lens is formed by the method described in [11].

BEST MODE FOR CARRYING OUT THE INVENTION

In a polymerizable composition comprising a thioepoxy compound having atleast one structure represented by formula (1), according to the presentinvention, the total content of a thioepoxy compound A, which has atleast one structure represented by formula (2) and at least onestructure represented by formula (3), and a thioepoxy compound B, whichhas at least one structure represented by formula (4) and at least onestructure represented by formula (3), is 4 mass percent or less withrespect to the total mass of the polymerizable composition, andpreferably, 2 mass percent or less. When the total content is 1.5 masspercent or less, it is more preferable. When the polymerizablecomposition is manufactured in this range, the refractive index and thehue of a resin to be formed are stabilized, and the optical strain isunlikely to be generated.

In formula (1), R₁ represents a divalent hydrocarbon group having 1 to10 carbon atoms, and in particular, there may be mentioned a linear,branched, or cyclic alkylene group having 1 to 10 carbon atoms; anarylene group having 6 to 10 carbon atoms such as phenylene, alkylsubstituted phenylene, and naphthalene; or an aralkylene group having 7to 10 carbon atoms, which is a combination of an alkylene group and anarylene group. Among those mentioned above, an alkylene group having 1to 10 carbon atoms is preferable. When methylene or ethylene is used, itis more preferable. When methylene is used, it is even more preferable.R₂, R₃, and R₄ each represent a hydrogen atom or a monovalenthydrocarbon group having 1 to 10 carbon atoms, and as the monovalenthydrocarbon having 1 to 10 carbon atoms, for example, a linear,branched, or cyclic alkyl group having 1 to 10 carbon atoms, an arylgroup having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10carbon atoms may be mentioned. Among those mentioned above, a hydrogenatom or an alkylene group having 1 to 10 carbon atoms is preferable.When a hydrogen atom or a methyl group is used, it is more preferable.When a hydrogen atom is used, it is even more preferable.

As the compound having at least one structure represented by formula(1), a compound primarily represented by formula (7) shown below ispreferable.

(Where R₅ to R₁₀ each represent a hydrocarbon group having 1 to 10carbon atoms or hydrogen. Y represents a substituted or unsubstituted,linear, branched, or cyclic divalent aliphatic hydrocarbon having 1 to10 carbon atoms, a substituted or unsubstituted 1,4-dithiane group, anarylene group, or an aralkylene group. m represents an integer of 0 to2, and n represents an integer of 0 to 4.)

In the above formula, R₅ to R₁₀ each have the same meaning as that of R₂to R₄ described above and, in particular, are each preferably a hydrogenatom. Y represents a substituted or unsubstituted, linear, branched, orcyclic divalent aliphatic hydrocarbon having 1 to 10 carbon atoms, asubstituted or unsubstituted 1,4-dithiane group, an arylene group, or anaralkylene group. As the divalent aliphatic hydrocarbon having 1 to 10carbon atoms, a linear, branched, or cyclic alkylene group having 1 to10 carbon atoms is preferable, and a linear alkylene group isparticularly preferable. As the arylene and the aralkylene groupsmentioned above, the same as those described for R₁ may be mentioned byway of example. In addition, Y may have a substituent group, and thesubstituent group is not specifically limited as long as properties(such as transparence, uniformity, refractive index, and heatresistance) of a resin manufactured from the compound described aboveare not adversely influenced thereby, and the substituent group maycomprise a reactive group. A compound having the structure representedby formula (1), and, in particular, a compound may be used which has atleast three functionalities and which comprises a 2,3-epithiopropylthiogroup as a substituent group; however, a compound having twofunctionalities is more preferable. Furthermore, a compound in which n=0is satisfied and/or a compound in which m=0 and n=1 are satisfied ismost preferable.

The thioepoxy compound having at least one intramolecular structurerepresented by formula (1), according to the present invention, such asa polythioepoxy compound represented by formula (7), can be derived froma polyepoxy compound having at least two functionalities. The polyepoxycompound can be easily obtained by a known method. For example, when apolythiol compound having a linear or branched alkyl sulfide structure;hydrogen sulfide, sodium hydrosulfide, or sodium sulfide; and anepihalohydrine compound, preferably, epichlorohydrine orepibromohydrine, are allowed to react with each other under the presenceof an alkali agent, an alkyl sulfide type epoxy compound represented byformula (8) is obtained.

(Where, Y, m, and n are the same as those described above.)

When the epoxy compound thus obtained is allowed to react with athiation agent selected, for example, from one of thiocyanic acid salts,thioureas, and triphenylphosphine sulfide, a polythioepoxy compoundrepresented by formula (9) is obtained. Among the thiation agents usedin this step, thiocyanic acid salts and thioureas are preferable. Inconsideration of reaction performance and cost, thiourea is morepreferable.

(Where, Y, m, and n are the same as those described above.)

As particular examples of polythiol compounds used as a startingmaterial, for example, there may be mentioned aliphatic thiols such as1,1-methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol,1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol,1,2,3-trimercaptopropane, tetrakis(mercaptomethyl)methane,1,2-dimercaptocyclohexane, bis(2-mercaptoethyl)sulfide,2,3-dimercapto-1-propanol, ethylene glycol bis(3-mercaptopropionate),diethylene glycol bis(3-mercaptopropionate), diethylene glycolbis(2-mercaptoglycolate), pentaerythritoltetrakis(2-mercaptothioglycolate), pentaerythritoltetrakis(3-mercaptopropionate), trimethylolpropanetris(2-mercaptothioglycolate), trimethylolpropanetris3-mercaptopropionate), 1,1,1-trimethylmercaptoethane,1,1,1-trimethylmercaptopropane, 2,5-dimercaptomethylthiophane,4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,2,5-dimercaptomethyl-1,4-dithiane,2,5-bis{(2-mercaptoethyl)thiomethyl}-1,4-dithiane,1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol,4,8-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, and5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane; and

aromatic thiols such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene,1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene,1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene,2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl,bis(4-mercaptophenyl)methane, bis(4-mercaptophenyl)sulfide,bis(4-mercaptophenyl)sulfone, 2,2-bis(4-mercaptophenyl)propane,1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, and1,2,5-trimercaptobenzene. However, the thiols are not limited to thosecompounds mentioned above.

In addition, as particular examples of polythioepoxy compounds, whichare represented by formula (5), obtained by thiation of polyepoxycompounds, for example, there may be mentioned acyclic aliphatic2,3-epithiopropylthio compounds such as bis(2,3-epithiopropyl)sulfide,bis(2,3-epithiopropyl)disulfide, bis(2,3-epithiopropylthio)methane,1,2-bis(2,3-epithiopropylthio)ethane,1,2-bis(2,3-epithiopropylthio)propane,1,3-bis(2,3-epithiopropylthio)propane,1,3-bis(2,3-epithiopropylthio)-2-methylpropane,1,4-bis(2,3-epithiopropylthio)butane,1,4-bis(2,3-epithiopropylthio)-2-methylbutane,1,3-bis(2,3-epithiopropylthio)butane,1,5-bis(2,3-epithiopropylthio)pentane,1,5-bis(2,3-epithiopropylthio)-2-methylpentane,1,5-bis(2,3-epithiopropylthio)-3-thiapentane,1,6-bis(2,3-epithiopropylthio)hexane,1,6-bis(2,3-epithiopropylthio)-2-methylhexane,3,8-bis(2,3-epithiopropylthio)-3,6-dithiaoctane,1,2,3-tris(2,3-epithiopropylthio)propane,2,2-bis(2,3-epithiopropylthio)-1,3-bis(2,3-epithiopropylthiomethyl)propane,2,2-bis(2,3-epithiopropylthiomethyl)-1-(2,3-epithiopropylthio)butane,1,5-bis(2,3-epithiopropylthio)-2-(2,3-epithiopropylthiomethyl)-3-thiapentane,1,5-bis(2,3-epithiopropylthio)-2,4-bis(2,3-epithiopropylthiomethyl)-3-thiapentane,1-(2,3-epithiopropylthio)-2,2-bis(2,3-epithiopropylthiomethyl)-4-thiahexane,1,5,6-tris(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl)-3-thiahexane,1,8-bis(2,3-epithiopropylthio)-4-(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-4,5-bis(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-4,4-bis(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-2,5-bis(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,8-bis(2,3-epithiopropylthio)-2,4,5-tris(2,3-epithiopropylthiomethyl)-3,6-dithiaoctane,1,1,1-tris[{2-(2,3-epithiopropylthio)ethyl}thiomethyl]-2-(2,3-epithiopropylthio)ethane,1,1,2,2-tetrakis[{2-(2,3-epithiopropylthio)ethyl}thiomethyl]ethane,1,11-bis(2,3-epithiopropylthio)-4,8-bis(2,3-epithiopropylthiomethyl)-3,6,9-trithiaundecane,1,11-bis(2,3-epithiopropylthio)-4,7-bis(2,3-epithiopropylthiomethyl)-3,6,9-trithiaundecane,and1,11-bis(2,3-epithiopropylthio)-5,7-bis(2,3-epithiopropylthiomethyl)-3,6,9-trithiaundecane;and

alicyclic 2,3-epithiopropylthio compounds such as1,3-bis(2,3-epithiopropylthio)cyclohexane,1,4-bis(2,3-epithiopropylthio)cyclohexane,1,3-bis(2,3-epithiopropylthiomethyl)cyclohexane,1,4-bis(2,3-epithiopropylthiomethyl)cyclohexane,2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane,2,5-bis[{2-(2,3-epithiopropylthio)ethyl}thiomethyl]-1,4-dithiane, and2,5-bis(2,3-epithiopropylthiomethyl)-2,5-dimethyl-1,4-dithiane; and

aromatic 2,3-epithiopropylthio compounds such as1,2-bis(2,3-epithiopropylthio)benzene,1,3-bis(2,3-epithiopropylthio)benzene,1,4-bis(2,3-epithiopropylthio)benzene,1,2-bis(2,3-epithiopropylthiomethyl)benzene,1,3-bis(2,3-epithiopropylthiomethyl)benzene,1,4-bis(2,3-epithiopropylthiomethyl)benzene,bis{4-(2,3-epithiopropylthio)phenyl}methane,2,2-bis{4-(2,3-epithiopropylthio)phenyl}propane,bis{4-(2,3-epithiopropylthio)phenyl}sulfide,bis{4-(2,3-epithiopropylthio)phenyl}sulfone, and4,4′-bis(2,3-epithiopropylthio)biphenyl. However, the polythioepoxycompounds are not limited to those compounds mentioned above. Among thecompounds mentioned above, bis(2,3-epithiopropyl)sulfide andbis(2,3-epithiopropyl)disulfide are preferable compounds, andbis(2,3-epithiopropyl)sulfide is more preferable compound.

As a method for manufacturing a polymerizable composition comprising acompound which has at least one structure represented by formula (1),according to the present invention, in which the total of the thioepoxycompound A and the thioepoxy compound B is 4 mass percent or less withrespect to the total mass of the polymerizable composition, among knownmethods for manufacturing a compound having at least one structurerepresented by formula (1) using a thiation agent and an acid or itsanhydride, a method for limiting the amounts of a thiation agent and anacid or its anhydride is effective, and a method for limitingtemperature conditions in addition to the amounts mentioned above ismost effective.

For example, when a polythioepoxy compound having the structurerepresented by formula (9) is manufactured from a polyepoxy compoundhaving the structure represented by formula (8), a method may bementioned in which the amounts of a thiation agent and an acid or itsanhydride for use are limited in consideration of epoxy equivalents ofthe polyepoxy compound and are then fed for reaction. In this case,although the amounts are not generally limited because of variousstructures and properties of epoxy compounds used as a startingmaterial, a thiation agent in an amount of 0.9 to 1.3 equivalents may beused with respect to one epoxy equivalent of a polyepoxy compound havingthe structure represented by formula (8). In this case, an amount of0.95 to 1.25 equivalents is preferably used. In addition, an amount of0.975 to 1.21 equivalents is more preferable.

As for an acid or its anhydride, 0.2 equivalents or less may be usedwith respect to one epoxy equivalent of a polyepoxy compound having thestructure represented by formula (8). In this case, an amount of 0.15equivalents or less is preferable. In addition, an amount of 0.1equivalents or less is more preferable.

The reaction temperature may be in the range of from 0 to 50° C., andpreferably, in the range of from 5 to 45° C. A reaction temperature of10 to 40° C. is more preferable.

In order to industrially control the reaction temperature as describedabove, one of a composition containing the polyepoxy compound and acomposition containing a thiation agent is preferably allowed to drip tothe other composition. In particular, it is more preferable that afterthe composition containing a thiation agent is placed still, thecomposition containing a polyepoxy compound be allowed to drip thereto.In this case, in the composition containing a polyepoxy compound,solvents, additives, water, and the like, which were used for synthesisthereof, may be contained, and from industrial point of view, thecomposition which still contains a solvent is preferably allowed to dripin terms of reaction efficiency, temperature control, and quality of anobtained thioepoxy compound.

As a reaction solvent used for thiation, a good result may be obtainedfrequently when a polar solvent alone or a mixture of a polar solventand a nonpolar solvent is used. In particular, as polar solvents, forexample, there may be mentioned alcohols such as water, methanol, andethanol; ketones such as acetone, methyl ethyl ketone, and methylisobutyl ketone; esters such as methyl acetate, ethyl acetate, propylacetate, and butyl acetate; ethers such as tetrahydrofuran; aproticpolar solvents such as dimethylformamide, dimethylimidazolidinone, anddimethyl sulfoxide. However, the polar solvents are not limited to thosementioned above. As nonpolar solvents, for example, there may bementioned aromatic hydrocarbons, such as benzene, toluene, and xylene,and halogen-substituted compound thereof; alicyclic hydrocarbons such ashexane and cyclohexane; and halogenated hydrocarbons such asdichloromethane, chloroform, and tetrachloromethane. However, thenonpolar solvents are not limited to those mentioned above.

As thiation agents used in this case, as is the case described above,for example, there may be mentioned thiocyanic acid salts, thioureas,and triphenylphosphine sulfide, and among those mentioned above,thiocyanic acid salts and thioureas are preferable. In consideration ofreaction performance and cost, thiourea is more preferable.

In order to suppress the variation in refractive index and opticalstrain of a polymerizable composition manufactured by the methoddescribed above, a compound represented by formula (5) shown below maybe mentioned as the thioepoxy compound A, the content of which islimited to a certain level.

(Where Y, m, n are the same as those described above)

As particular examples of the thioepoxy compound A, there may bementioned acyclic aliphatic (2,3-epithiopropyl)thio compounds having a(2,3-epidithiopropylthio group) structure represented by formula (2),such as 2,3-epidithiopropyl(2,3-epithiopropyl)sulfide,2,3-epidithiopropyl(2,3-epithiopropyl)disulfide,2,3-epidithiopropyl(2,3-epithiopropyl)thiomethane,1-(2,3-epidithiopropylthio)-2-(2,3-epithiopropyl)thioethane,1-(2,3-epidithiopropylthio)-2-(2,3-epithiopropyl)thiopropane,1-(2,3-epidithiopropylthio)-3-(2,3-epithiopropyl)thiopropane,1-(2,3-epidithiopropylthio)-3-(2,3-epithiopropyl)thio-2-methylpropane,1-(2,3-epidithiopropylthio)-4-(2,3-epithiopropyl)thiobutane,1-(2,3-epidithiopropylthio)-4-(2,3-epithiopropyl)thio-2-methylbutane,1-(2,3-epidithiopropylthio)-3-(2,3-epithiopropyl)thiobutane,1-(2,3-epidithiopropylthio)-5-(2,3-epithiopropyl)thiopentane,1-(2,3-epidithiopropylthio)-5-(2,3-epithiopropyl)thio-2-methylpentane,1-(2,3-epidithiopropylthio)-5-(2,3-epithiopropyl)thio-3-thiapentane,1-(2,3-epidithiopropylthio)-6-(2,3-epithiopropyl)thiohexane,1-(2,3-epidithiopropylthio)-6-(2,3-epithiopropyl)thio-2-methylhexane,and1-(2,3-epidithiopropylthio)-8-(2,3-epithiopropyl)thio-3,6-dithiaoctane;and

alicyclic (2,3-epithiopropyl)thio compounds having a(2,3-epidithiopropylthio group) structure represented by formula (2),such as1-(2,3-epidithiopropylthio)-3-(2,3-epithiopropyl)thiocyclohexane,1-(2,3-epidithiopropylthio)-4-(2,3-epithiopropyl)thiocyclohexane,1-(2,3-epidithiopropylthiomethyl)-3-(2,3-epithiopropyl)thiomethylcyclohexane,1-(2,3-epidithiopropylthiomethyl)-4-(2,3-epithiopropyl)thiomethylcyclohexane,2-(2,3-epidithiopropylthiomethyl)-5-(2,3-epithiopropyl)thiomethyl-1,4-dithiane,2-{(2-(2,3-epidithiopropylthioethyl)thio)ethyl}-5-{2-(2,3-epithiopropyl)thioethyl}thiomethyl-1,4-dithiane,and2-(2,3-epidithiopropylthiomethyl)-5-(2,3-epithiopropyl)thiomethyl-2,5-dimethyl-1,4-dithiane;and

aromatic (2,3-epithiopropyl)thio compounds having a(2,3-epidithiopropylthio group) structure represented by formula (2),such as 1-(2,3-epidithiopropylthio)-2-(2,3-epithiopropyl)thiobenzene,1-(2,3-epidithiopropylthio-)3-(2,3-epithiopropyl)thiobenzene,1-(2,3-epidithiopropylthio)-4-(2,3-epithiopropyl)thiobenzene,1-(2,3-epidithiopropylthiomethyl)-2-(2,3-epithiopropyl)thiomethylbenzene,1-(2,3-epidithiopropylthiomethyl)-3-(2,3-epithiopropyl)thiomethylbenzene,1-(2,3-epidithiopropylthiomethyl)-4-(2,3-epithiopropyl)thiomethylbenzene,{4-(2,3-epithiopropylthio)phenyl-4′-(2,3-epidithiopropylthio)phenyl}methane,2,2-{4-(2,3-epithiopropylthio)phenyl-4′-(2,3-epidithiopropylthio)phenyl}propane,{4-(2,3-epithiopropyl)thiophenyl-4′-(2,3-epidithiopropylthio)phenyl}sulfide,{4-(2,3-epithiopropylthio)phenyl-4′-(2,3-epidithiopropylthio)phenyl}sulfone,4-(2,3-epithiopropylthio)-4′-(2,3-epidithiopropylthio)biphenyl, and4-(2,3-epithiopropylthio)-4′-(2,3-epidithiopropylthio)phenyl sulfide.However, the thioepoxy compound A is not limited to the compoundsmentioned above.

In addition, as the thioepoxy compound B, for example, a compoundrepresented by formula (6) may be mentioned.

(Where Y, m, and n are the same as those described above)

As particular examples of the thioepoxy compound B, there may bementioned acyclic aliphatic (2,3-epithiopropyl)thio compounds having a(2,3-epoxypropylthio group) structure represented by formula (4), suchas 2,3-epoxypropyl(2,3-epithiopropyl)sulfide,2,3-epoxypropyl(2,3-epithiopropyl)disulfide,2,3-epoxypropylthio(2,3-epithiopropyl)thiomethane,1-(2,3-epoxypropylthio)-2-(2,3-epithiopropyl)thioethane,1-(2,3-epoxypropylthio)-2-(2,3-epithiopropyl)thiopropane,1-(2,3-epoxypropylthio)-3-(2,3-epithiopropyl)thiopropane,1-(2,3-epoxypropylthio)-3-(2,3-epithiopropyl)thio-2-methylpropane,1-(2,3-epoxypropylthio)-4-(2,3-epithiopropyl)thiobutane,1-(2,3-epoxypropylthio)-4-(2,3-epithiopropyl)thio-2-methylbutane,1-(2,3-epoxypropylthio)-3-(2,3-epithiopropyl)thiobutane,1-(2,3-epoxypropylthio)-5-(2,3-epithiopropyl)thiopentane,1-(2,3-epoxypropylthio)-5-(2,3-epithiopropyl)thio-2-methylpentane,1-(2,3-epoxypropylthio)-5-(2,3-epithiopropyl)thio-3-thiapentane,1-(2,3-epoxypropylthio)-6-(2,3-epithiopropyl)thiohexane,1-(2,3-epoxypropylthio)-6-(2,3-epithiopropyl)thio-2-methylhexane, and1-(2,3-epoxypropylthio)-8-(2,3-epithiopropyl)thio-3,6-dithiaoctane; and

alicyclic (2,3-epithiopropyl)thio compounds having a(2,3-epoxypropylthio group) structure represented by formula (4), suchas 1-(2,3-epoxypropylthio)-3-(2,3-epithiopropyl)thiocyclohexane,1-(2,3-epoxypropylthio)-4-(2,3-epithiopropyl)thiocyclohexane,1-(2,3-epoxypropylthiomethyl)-3-(2,3-epithiopropyl)thiomethylcyclohexane,1-(2,3-epoxypropylthiomethyl)-4-(2,3-epithiopropyl)thiomethylcyclohexane,2-(2,3-epoxypropylthiomethyl)-5-(2,3-epithiopropyl)thiomethyl-1,4-dithiane,2-{(2-(2,3-epoxypropylthioethyl)thio)ethyl}-5-{2-(2,3-epithiopropyl)thioethyl}thiomethyl-1,4-dithiane,and2-(2,3-epoxypropylthiomethyl)-5-(2,3-epithiopropyl)thiomethyl-2,5-dimethyl-1,4-dithiane;and

aromatic (2,3-epithiopropyl)thio compounds having a (2,3-epoxypropylthiogroup) structure represented by formula (4), such as1-(2,3-epoxypropylthio)-2-(2,3-epithiopropyl)thiobenzene,1-(2,3-epoxypropylthio-)3-(2,3-epithiopropyl)thiobenzene,1-(2,3-epoxypropylthio)-4-(2,3-epithiopropyl)thiobenzene,1-(2,3-epoxypropylthiomethyl)-2-(2,3-epithiopropyl)thiomethylbenzene,1-(2,3-epoxypropylthiomethyl)-3-(2,3-epithiopropyl)thiomethylbenzene,1-(2,3-epoxypropylthiomethyl)-4-(2,3-epithiopropyl)thiomethylbenzene,{4-(2,3-epithiopropylthio)phenyl-4′-(2,3-epoxypropylthio)phenyl}methane,2,2-{4-(2,3-epithiopropyl)thiophenyl-4′-(2,3-epoxypropylthio)phenyl}propane,{4-(2,3-epithiopropyl)thiophenyl-4′-(2,3-epoxypropylthio)phenyl}sulfide,{4-(2,3-epithiopropylthio)phenyl-4′-(2,3-epoxypropylthio)phenyl}sulfone,4-(2,3-epithiopropylthio)-4′-(2,3-epoxypropylthio)biphenyl, and4-(2,3-epithiopropylthio)-4′-(2,3-epoxypropylthio)phenyl sulfide.However, the thioepoxy compound B is not limited to the compoundsmentioned above.

The polymerizable composition according to the present invention, whichcomprises a compound having at least one structure represented byformula (1), is a polymerizable composition in which the total of thethioepoxy compound A and the thioepoxy compound B is 4 mass percent orless with respect to the total mass of the polymerizable composition,and in this polymerizable composition, polysulfide oligomers such asdimmers, trimers, tetramers of the compound mentioned above; inorganicacids and organic acids added as a polymerization inhibitor; organiccompounds such as a solvent and other by-products; and inorganiccompounds may be contained as long as they may not cause any problems.

The polymerizable composition according to the present invention may beused for a resin having an intermediate refractive index in addition toa resin having a high refractive index, and in order to primarilycontrol various properties of an obtained resin, such as impactresistance and specific gravity, and/or to control monomer viscosity andother handling properties, a resin modifier may be added for improvementof the resin.

As resin modifiers, in addition to the components added to thepolymerizable composition of the present invention, for example, theremay be mentioned thioepoxy compounds, thiol compounds,iso(thio)cyanates, mercapto organic acids, organic acids and anhydridesthereof, amino acids and mercaptoamines, amines, and olefins containing(meth)acrylates.

As particular examples of thiol compounds used as a resin modifier, forexample, there may be mentioned aliphatic thiols such as methylmercaptan, ethyl mercaptan, 1,1-methanedithiol, 1,2-ethanedithiol,1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol,1,4-butanedithiol, 1,2,3-trimercaptopropane,tetrakis(mercaptomethyl)methane, 1,2-dimercaptocyclohexane,bis(2-mercaptoethyl)sulfide, 2,3-dimrcapto-1-propanol, ethylene glycolbis(3-mercaptopropionate), diethylene glycol bis(3-mercaptopropionate),diethylene glycol bis(2-mercaptoglycolate), pentaerythritoltetrakis(2-mercaptothioglycolate), pentaerythritoltetrakis(3-mercaptopropionate), trimethylolpropanetris(2-mercaptothioglycolate), trimethylolpropanetris3-mercaptopropionate), 1,1,1-trimethylmercaptoethane,1,1,1-trimethylmercaptopropane, 2,5-dimercaptomethylthiophane,4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,2,5-dimercaptomethyl-1,4-dithiane,2,5-bis{(2-mercaptoethyl)thiomethyl}-1,4-dithiane,1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol,4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane,4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; and

aromatic thiols such as benzylthiol, thiophenol, 1,2-dimercaptobenzene,1,3-dimercaptobenzene, 1,4-dimercaptobenzene,1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene,1,4-bis(mercaptomethyl)benzene, 2,2′-dimercaptobiphenyl,4,4′-dimercaptobiphenyl, bis(4-mercaptophenyl)methane,bis(4-mercaptophenyl)sulfide, bis(4-mercaptophenyl)sulfone,2,2-bis(4-mercaptophenyl)propane, 1,2,3-trimercaptobenzene,1,2,4-trimercaptobenzene, and 1,2,5-trimercaptobenzene. However, thethiol compounds are not limited to the compounds mentioned above.

As particular examples of iso(thio)cyanate compounds used as a resinmodifier, for example, there may be mentioned monofunctional isocyanatessuch as methyl isocyanate, ethyl isocyanate, n-propyl isocyanate,isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate,tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptylisocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate,myristyl isocyanate, octadecyl isocyanate, 3-pentyl isocyanate,2-ethylhexyl isocyanate, 2,3-dimethylcyclohexyl isocyanate,2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, α-methylbenzylisocyanate, phenylethyl isocyanate, phenyl isocyanate, o-, m-, orp-tolyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, and(isocyanatomethyl)bicycloheptane;

aliphatic polyisocyanate compound such as hexamethylene diisocyanate,2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate,butene diisocyanate, 1,3-butadiene-1,4-diisocyanate,2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 1,3,6-hexamethylene triisocyanate,1,8-diisocyanato-4-isocyanatomethyloctane,bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, lysinediisocyanatomethyl ester, lysine triisocyanate, xylylene diisocyanate,bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene,α,α,α′,α′-tetramethylxylylene diisocyanate, bis(isocyanatobutyl)benzene,bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether,bis(isocyanatoethyl)phthalate, mesitylylene triisocyanate, and2,6-di(isocyanatomethyl)furan;

alicyclic polyisocyanate compounds such as isophorone diisocyanate,bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate,cyclohexane diisocyanate, methylcyclohexane diisocyanate,dicyclohexyldimethylmethane diisocyanate,2,2-dimethyldicyclohexylmethane diisocyanate,2,5-bis(isocyanatomethyl)bicyclo-[2,2,1]-heptane,2,6-bis(isocyanatomethyl)bicyclo-[2,2,1]-heptane, 3,8-bis(isocyanatomethyl)tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, and4,9-bis(isocyanatomethyl)tricyclodecane;

aromatic polyisocyanate compounds such as phenylene diisocyanate,tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylenediisocyanate, dimethylphenylene diisocyanate, diethylphenylenediisocyanate, diisopropylphenylene diisocyanate, trimethylbenzenetriisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidinediisocyanate, 4,4-diphenylmethane diisocyanate,3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate,bis(isocyanatophenyl)ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate,phenylisocyanatoethyl isocyanate, hexahydrobenene diisocyanate, andhexahydrodiphenylmethane-4,4-diisocyanate;

sulfur-containing aliphatic polyisocyanate compounds such asbis(isocyanatomethyl)sulfide, bis (isocyanatoethyl) sulfide, bis(isocyanatopropyl) sulfide, bis(isocyanatehexyl)sulfide,bis(isocyanatomethyl)sulfone, bis(isocyanatomethyl)disulfide,bis(isocyanatoethyl)disulfide, bis(isocyanatopropyl)disulfide,bis(isocyanatomethylthio) methane, bis(isocyanatoethylthio)methane,bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane, and1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane;

aromatic sulfide-type polyisocyanate compounds such asdiphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate,3,3-dimethoxy-4,4-diisocyanatodibenzyl thioether,bis(4-isocyanatomethylbenzene)-sulfide, and4,4-methoxybenzene-thioethyleneglycol-3,3-diisocyanate;

aromatic disulfide-type polyisocyanates such asdiphenyldisulfide-4,4-diisocyanate,2,2-dimethyldiphenyldisulfide-5,5-diisocyanate,3,3-dimethyldiphenyldisulfide-5,5-diisocyanate,3,3-dimethyldiphenyldisulfide-6,6-diisocyanate,4,4-dimethyldiphenyldisulfide-5,5-diisocyanate,3,3-dimethoxydiphenyldisulfide-4,4-diisocyanate, and4,4-dimethoxydiphenyldisulfide-3,3-diisocyanate;

-   -   sulfur-containing heterocyclic compounds such as        2,5-diisocyanatothiophene and        2,5-bis(isocyanatomethyl)thiophene; and

others such as 2,5-diisocyanatotetrahydrothiophene,2,5-bis(isocyanatomethyl)tetrahydrothiophene,3,4-bis(isocyanatomethyl)tetrahydrothiophene,2,5-diisocyanato-1,4-dithiane, 2,5-bis(isocyanatomethyl)-1,4-dithiane,4,5-diisocyanato-1,3-dithiolane,4,5-bis(isocyanatomethyl)-1,3-dithiolane, and4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithiolane. However, theiso(thio)cyanate compounds are not limited to the compounds mentionedabove. In addition, as usable materials based on the compounds mentionedabove, for example, there may be mentioned halogen-substituted compoundssuch as chlorine-substituted or bromine-substituted compounds,alkyl-substituted compounds, alkoxy-substituted compounds,nitro-substituted compounds, prepolymer-type modified compounds formedwith polyols, carbodiimide modified compounds, urea modified compounds,biuret-modified compounds, and products obtained by dimerization andtrimerization reactions.

Furthermore, as particular examples of isothiocyanate compounds, forexample, there may be mentioned monofunctional isothiocyanate compoundssuch as methyl isothiocyanate, ethyl isothiocyanate, n-propylthioisocyanate, isopropyl isothiocyanate, n-butyl isothiocyanate,sec-butyl isothiocyanate, tert-butyl isothiocyanate, pentylisothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octylisothiocyanate, decyl isothiocyanate, lauryl isothiocyanate, myristylisothiocyanate, octadecyl isothiocyanate, 3-pentyl isothiocyanate,2-ethylhexyl isothiocyanate, 2,3-dimethylcyclohexyl isothiocyanate,2-methoxyphenyl isothiocyanate, 4-methoxyphenyl isothiocyanate,α-methylbenzyl isothiocyanate, phenylethyl isothiocyanate, phenylisothiocyanate, o-, m- or p-tolyl isothiocyanate, cyclohexylisothiocyanate, benzyl isothiocyanate, and(isothiocyanatomethyl)bicycloheptane;

aliphatic polyisothiocyanate compounds such as1,6-diisothiocyanatohexane and p-phenyleneisopropylidenediisothiocyanate; alicyclic polyisothiocyanate compounds such ascyclohexane diisothiocyanate and (diisothiocyanato)methylbicycloheptane;

aromatic isothiocyanate compounds such as 1,2-diisothiocyanatobenzene,1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene,2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene,4,4-diisothiocyanato-1,1-biphenyl,1,1-methylene-bis(4-isothiocyanatobenzene),1,1-methylene-bis(4-isothiocyanato-2-methylbenzene),1,1-methylene-bis(4-isothiocyanato-3-methylbenzene),1,1-(1,2-ethanediyl)bis(isothiocyanatobenzene),4,4-diisothiocyanatobenzophenone,4,4-diisothiocyanato-3,3-dimethylbenzophenone, diphenylether-4,4-diisothiocyanate, and diphenylamine-4,4-diisothiocyanate; and

furthermore, carbonylisothiocyanate compounds such as1,3-benzenedicarbonyl diisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, and (2,2-pyridine)-4,4-dicarbonyl diisothiocyanate.However, the isothiocyanate compounds are not limited to the compoundsmentioned above.

As particular examples of isothiocyanate compounds containing at leastone sulfur atom in addition to an isothiocyanate group, for example,there may be mentioned sulfur-containing aliphatic isothiocyanatecompounds such as thiobis(3-isothiocyanatopropane),thiobis(2-isothiocyanatoethane), and dithiobis(2-isothiocyanatoethane);sulfur-containing aromatic isothiocyanate compounds such as1-isothiocyanato-4-[(2-isothiocyanato)sulfonyl]benzene,thiobis(4-isothiocyanatobenzene), sulfonylbis(4-isothiocyanatobenzene),and dithiobis(4-isothiocyanatobenzene); and sulfur-containingheterocyclic isothiocyanate compounds such as2,5-diisothiocyanatothiophene and 2,5-diisothiocyanato-1,4-dithiane.However, the isothiocyanate compounds containing at least one sulfuratom, mentioned above, are not limited to those mentioned above.

In addition, as usable materials based on the compounds mentioned above,for example, there may be mentioned halogen-substituted compounds suchas chlorine-substituted or bromine-substituted compounds,alkyl-substituted compounds, alkoxy-substituted compounds,nitro-substituted compounds, prepolymer-type modified compounds formedwith polyols, carbodiimide modified compounds, urea modified compounds,biuret-modified compounds, and products obtained by dimerization andtrimerization reactions.

Furthermore, isothiocyanate compounds having an isocyanate group mayalso be mentioned. For example, there may be mentioned aliphatic andalicyclic compounds such as 1-isocyanato-6-isothiocyanatohexane and1-isocyanato-4-isothiocyanatocyclohexane; aromatic compounds such as1-isocyanato-4-isothiocyanatobenzene and4-methyl-3-isocyanato-1-isothiocyanatobenzene; and heterocycliccompounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine; and

sulfur-containing compounds in addition to an isothiocyanate group, suchas 4-isocyanato-4′-isothiocyanatodiphenyl sulfide and2-isocyanato-2′-isothiocyanatodiethyl disulfide. However, theisothiocyanate compounds having an isocyanate group are not limited tothose compounds mentioned above.

In addition, for example, as usable materials based on the compoundsmentioned above, there may be mentioned halogen-substituted compoundssuch as chlorine-substituted or bromine-substituted compounds,alkyl-substituted compounds, alkoxy-substituted compounds,nitro-substituted compounds, prepolymer-type modified compounds formedwith polyols, carbodiimide modified compounds, urea modified compounds,biuret-modified compounds, and products obtained by dimerization andtrimerization reactions.

As particular examples of mercapto organic acids, for example, there maybe mentioned thioglycolic acid, 3-mercaptopropionic acid, thioaceticacid, thiolactic acid, thiomalic acid, and thiosalicylic acid, and asparticular examples of organic acids and anhydrides thereof, forexample, there may be mentioned, in addition to the polymerizationinhibitors mentioned above, thiodiglycolic acid, thiodipropionic acid,dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride,methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride,methylnorbornenic anhydride, methylnorbornanic anhydride, maleicanhydride, trimellitic anhydride, and pyromellitic anhydride. However,the mercapto organic acids and the organic acids and the anhydridesthereof are not limited to those compounds mentioned above.

As particular examples of amine compounds, for example, there may bementioned monofunctional primary amine compounds such as ethylamine,n-propylamine, isopropylamine, n-butylamine, sec-butylamine,tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine,decylamine, laurylamine, myristylamine, 3-pentylamine,2-ethyl-hexylamine, 1,2-dimethylhexylamine, allylamine,aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine,2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline,benzylamine, phenetylamine, 2-, 3-, or 4-methylbenzylamine, o-, m-, orp-methylaniline, o-, m-, or p-ethylaniline, aminomorpholine,naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine,aminopyridine, aminophenol, aminoethanol, 1-aminopropanol,2-aminopropanol, aminobutanol, aminopentanol, aminohexanol,methoxyethylamine, 2-(2-aminoethoxy)ethanol, 3-ethoxypropylamine,3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine,3-isobutoxypropylamine, and 2,2-diethoxyethylamine;

primary polyamine compounds such as ethylenediamine, 1,2- or1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1,5-diaminopentane,1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane,1,10-diaminodecane, 1,2-, 1,3- or 1,4-diaminocyclohexane, o-, m- orp-diaminobenzene, 3,4- or 4,4′-diaminobenzophenone, 3,4- or4,4′-diaminodiphenylether, 4,4′-diaminodiphenylmethane,4,4′-diaminodiphenylsulfide, 3,3′- or 4,4′-diaminodiphenylsulfone,2,7-diaminofluorene, 1,5-, 1,8- or 2,3-diaminonaphthalene, 2,3-, 2,6- or3,4-diaminopyridine, 2,4- or 2,6-diaminotoluene, m-, orp-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3-or 1,4-diaminomethylcyclohexane, 2- or 4-aminopiperidine, 2- or4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine,N-aminoethylmorpholine, and N-aminopropylmorpholine; and

monofunctional secondary amine compounds such as diethylamine,dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine,di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine,di(2-ethylhexyl)amine, methylhexylamine, diallylamine,N-methylallylamine, piperidine, pyrrolidine, diphenylamine,N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine,N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N-ethylaniline,dinaphthylamine, 1-methylpiperazine, and morpholine; and

secondary polyamine compounds such as N,N′-dimethyl-ethylenediamine,N,N′-dimethyl-1,2-diaminopropane, N,N′-dimethyl-1,3-diaminopropane,N,N′-dimethyl-1,2-diaminobutane, N,N′-dimethyl-1,3-diaminobutane,N,N′-dimethyl-1,4-diaminobutane, N,N′-dimethyl-1,5-diaminopentane,N,N′-dimethyl-1,6-diaminohexane, N,N′-dimethyl-1,7-diaminoheptane,N,N′-diethylethylenediamine, N,N′-diethyl-1,2-diaminopropane,N,N′-diethyl-1,3-diaminopropane, N,N′-diethyl-1,2-diaminobutane,N,N′-diethyl-1,3-diaminobutane, N,N′-diethyl-1,4-diaminobutane,N,N′-diethyl-1,5-diaminopentane, N,N′-diethyl-1,6-diaminohexane,N,N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine,2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine,1,1-di(4-piperidyl)methane, 1,2-di(4-piperidyl)ethane,1,3-di(4-piperidyl)propane, 1,4-di(4-piperidyl)butane, andtetramethylguanidine. However, the amine compounds are not limited tothose mentioned above.

As particular examples of olefins, for example, there may be mentioned(meth)acrylate compounds such as benzyl acrylate, benzyl methacrylate,butyxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate,cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethylmethacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethylacrylate, phenoxyethyl methacrylate, phenyl methacrylate,3-phenoxy-2-hydroxypropyl acrylate, ethylene glycol diacrylate, ethyleneglycol dimethacrylate, diethylene glycol diacrylate, diethylene glycoldimethacrylate, triethylene glycol diacrylate, triethylene glycoldimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycoldimethacrylate, polyethylene glycol diacrylate, polyethylene glycoldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycolbisglycidyl methacrylate, bisphenol-A diacrylate, bisphenol-Adimethacrylate, 2,2-bis(4-acryloxyethoxyphenyl)propane,2,2-bis(4-methacryloxyethoxyphenyl)propane,2,2-bis(4-acryloxydiethoxyphenyl)propane,2,2-bis(4-methacryloxydiethoxyphenyl)propane, bisphenol-F diacrylate,bisphenol-F dimethacrylate, 1,1-bis(4-acryloxyethoxyphenyl)methane,1,1-bis(4-methacryloxyethoxyphenyl)methane,1,1-bis(4-acryloxydiethoxyphenyl)methane,1,1-bis(4-methacryloxydiethoxyphenyl)methane, dimethyloltricyclodecanediacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, glycerol diacrylate, glycerol dimethacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,pentaerythritol tetramethacrylate, methylthio acrylate, methylthiomethacrylate, phenylthio acrylate, benzylthio methacrylate,xylenedithiol diacrylate, xylenedithiol dimethacrylate,mercaptoethylsulfide diacrylate, and mercaptoethylsulfidedimethacrylate; allyl compounds such as allyl glycidyl ether, diallylphthalate, diallyl terephthalate, diallyl isophthalate, diallylcarbonate, and diethylene glycol bisallyl carbonate; vinyl compoundssuch as styrene, chlorostyrene, methylstyrene, bromostyrene,dibromostyrene, divinylbenzene, and 3,9-divinyl-spiro-bi(m-dioxane); anddiisopropenylbenzene. However, the olefin compounds are not limited tothose mentioned above.

The resin modifiers mentioned above may be used alone or in combination.

As curing catalysts used in this invention, for example, tertiaryamines, phosphines, quaternary ammonium salts, quaternary phosphoniumsalts, Lewis acids, radical polymerization catalysts, and cationicpolymerization catalysts are generally used.

As particular examples of curing catalysts, for example, there may bementioned tertiary amines such as triethylamine, tri-n-butylamine,tri-n-hexylamine, N,N-diisopropylethylamine, triethylenediamine,triphenylamine, N,N-dimethylethanolamine, N,N-diethylethanolamine,N,N-dibutylethanolamine, N,N-dimethylbenzylamine, diethylbenzylamine,N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine,N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine,pyridine, N,N-dimethylaniline, β-picoline, N,N′-dimethylpiperazine,N-methylpiperizine, 2,2′-bipyridyl, hexamethylenetetramine, and1,8-diazabicyclo(5.4.0)-7-undecene; phosphines such astrimethylphosphine, triethylphosphine, tri-n-propylphosphine,triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine,tribenzylphosphine, 1,2-bis(diphenylphosphino)ethane, and1,2-bis(dimethylphosphino)ethane; quaternary ammonium salts such astetramethylammonium bromide, tetrabutylammonium chloride, andtetrabutylammonium bromide; quaternary phosphonium salts such astetramethylphosphonium bromide, tetrabutylphosphonium chloride, andtetrabutylphosphonium bromide; Lewis acids such as dimethyltindichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrachlorotin,dibutyltin oxide, diacetoxytetrabutyl distannoxane, zinc chloride, zincacetylacetonate, aluminum chloride, aluminum fluoride,triphenylaluminum, titanium tetrachloride, and calcium acetate; radicalpolymerization catalysts such as2,2′-azobis(2-cyclopropylpropionitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis(2,4-dimethylvaleronitrile), t-butylperoxy-2-ethyl hexanoate,n-butyl-4,4′-bis(t-butylperoxy)valerate, and t-butyl peroxybenzoate; andcationic polymerization catalysts such as diphenyliodoniumhexafluorophosphate, diphenyliodonium hexafluoroarsenate,diphenyliodonium hexafluoroantimony, triphenylsulfoniumtetrafluoroborate, triphenylsulfonium hexafluorophosphate, andtriphenylsulfonium hexafluoroarsenate. However, the curing catalysts arenot limited to those mentioned above. Preferable compounds among thosementioned above are tertiary amine compounds, phosphine compounds,quaternary ammonium salts, and quaternary phosphonium salts.

The curing catalysts mentioned above may be used alone or incombination.

When an amount of the curing catalyst of 0.001 to 1 mass percent is usedwith respect to the total mass of a polymerizable composition containinga thioepoxy compound, preferable pot life and properties of an obtainedresin, such as transparence, optical properties, and weatherability maybe obtained. In addition, an amount of 0.01 to 5 mass percent is morepreferably used.

As a typical polymerization method for obtaining a resin (plastic lensor the like) of the present invention, for example, cast polymerizationmay be mentioned. That is, a polymerizable composition containing athioepoxy compound and a curing catalyst is poured between mold platesheld by a gasket or a tape. In this step, defoaming or the like may beperformed whenever necessary and it may not cause any problems at all.

Next, heating is performed in a heating device, that is, in an oven orin water, for curing, and the resin can then be demolded.

Since the type and the amount of catalyst or the like and the type andratio of monomers, which are used for obtaining the resin of the presentinvention, vary in accordance with each own polymerizable composition,they cannot be generally determined.

Since heating conditions for polymerizing the polymerizable compositionof the present invention poured into a cast mold largely depend on thetype of thioepoxy compound, the type of curing catalyst, the shape ofthe mold, and the like, they cannot be generally determined; however,heating is performed at approximately −50 to 200° C. for 1 to 100 hours.

Preferable results may be obtained in some cases when the temperature isheld or is gradually increased in the range of from 10° C. to 150° C.for 1 to 80 hours for polymerization.

In addition, when the polymerizable composition of the present inventionis irradiated with energy rays such as ultraviolet rays or electronbeams, the polymerization time can be decreased. In the case describedabove, a curing catalyst such as a radical polymerization catalyst or acationic polymerization catalyst may be required in some cases.

When a resin of the present invention is molded, in accordance withindividual purposes, as is the case of known molding methods, variousmaterials such as chain extenders, cross-linking agents,photostabilizers, UV absorbers, antioxidants, anti-coloring agents,dyes, fillers, external and internal mold release agents, and adhesionimprovers may be added.

In addition, a demolded resin may be processed by annealing or the likewhenever necessary.

A resin obtained by curing the polymerizable composition of the presentinvention is a very superior transparent resin in which variations inhue and refractive index are not observed and the optical strain doesnot exist. Various forms of the resin described above can be obtained asa molded substance by changing a mold used for cast molding, and themolded substance can be used as a transparent resin for variousapplications, such as a material for optical elements, which requirestable refractive indices, including glass lenses, camera lenses, andlight-emitting diodes (LED). In particular, they can be preferably usedas an optical material for glass lenses, camera lenses, and the like.

Furthermore, for example, in order to improve antireflection,anti-abrasion, or chemical resistance, or in order to impart highhardness, antifoggy properties, and cosmetic properties, lenses obtainedfrom the resin of the present invention can be processed by physical orchemical treatment such as surface polishing, antistatic treatment, hardcoating, non-reflection coating, or dyeing.

EXAMPLES

Hereinafter, the present invention will be described in more detail withreference to examples. Among performance evaluations of the resinobtained in the examples, the refractive index and the optical strainwere evaluated by the following methods.

-   -   Refractive Index (ne): Measurement was performed at a        temperature of 20° C. using a Pulfrich refractometer.    -   Hue: When a YI value of a resin, measured by a calorimeter, was        different by ±1 or more from a value (described in Examples 1        and 4) obtained by curing a specific polymerizable composition,        the resin was regarded as x (not good), and when the YI value is        less than that, the resin is regarded as o (good). The specific        polymerizable composition mentioned above was a polymerizable        composition containing a compound which has at least one        structure represented by formula (1), in which the total content        of a thioepoxy compound, which has at least one intramolecular        structure represented by formula (2) and at least one        intramolecular structure represented by formula (3), and a        thioepoxy compound, which has at least one intramolecular        structure represented by formula (4) and at least one        intramolecular structure represented by formula (3), was 0 with        respect to the total amount of the polymerizable composition.    -   Optical strain: Observation was performed by visual inspection        using a high pressure mercury lamp. A resin having an optical        strain was represented by x (not good), and a resin having no        strain was represented by o (good).

In the examples, as a thioepoxy compound having at least one structurerepresented by formula (1), bis(2,3-epithiopropyl)disulfide (called acompound (a)) and bis(2,3-epithiopropyl)sulfide (called a compound (b))were used; as by-produced impurities, that is, as the thioepoxy compoundhaving at least one intramolecular structure represented by formula (2)and at least one intramolecular structure represented by formula (3),2,3-epidithiopropyl(2,3-epithiopropyl)disulfide (called a compound (c))and 2,3-epidithiopropyl(2,3-epithiopropyl)sulfide (called a compound(d)) were used; and as the thioepoxy compound having at least oneintramolecular structure represented by formula (4) and at least oneintramolecular structure represented by formula (3),2,3-epoxypropyl(2,3-epithiopropyl)disulfide (called a compound (e)) and2,3-epoxypropyl(2,3-epithiopropyl)sulfide (called a compound (f)) wereused. Impurity analysis of the compounds mentioned above andpolymerization of a polymerizable composition formed of the compositiondescribed above were performed, and the evaluations were then carriedout. In addition, after the compound (c), the compound (d), the compound(e), and the compound (f) were synthesized and isolated as describedbelow, the structures were determined beforehand, and analytical factorsthereof were also determined.

Synthesis Example 1 Synthesis of Compound (c)

After 1,000 ml of methanol and 3.5 g of calcium hydroxide were chargedin a reactor provided with a stirrer and a thermometer, 450 g of ahydrogen sulfide gas was introduced thereinto for 6 hours while 555 g ofepichlorohydrine was added dropwise. In this step, the solution in thereactor was always maintained at a temperature of 0° C. to 5° C. Afterthe reaction was finished, the hydrogen sulfide gas was removed, and themethanol was then removed by distillation, 760 g of crude1-chloro-3-mercapto-2-propanol was obtained. The compound thus obtainedwas processed by simple distillation, thereby obtaining a compoundhaving a purity of 99%. Next, particles of solid iodine were addedstepwise to a mixture of 250 g of this distillated material, water,methanol, and 180 g of sodium bicarbonate. Next, after toluene and 350 gof a sodium hydroxide solution at a concentration of 25% were added, themixture thus formed was held for 3 hours for aging. After an organiclayer obtained through the aging was washed with water twice, 130 g ofthiourea, 5 g of acetic acid, and methanol were added thereto, and themixture thus formed was stirred for 16 hours at a temperature of 25° C.After aging, a toluene layer was washed with an aqueous solutioncontaining sodium chloride, thereby obtaining a toluene layer containingthe compound (a). Next, 130 g of thiourea, 5 g of acetic acid, andmethanol were mixed with this toluene layer thus obtained and were thenstirred for 6 hours at a temperature of 25° C. After aging, the toluenelayer thus obtained was washed with an aqueous solution containingsodium chloride, thereby obtaining a toluene layer containing thecompound (c). After the toluene layer was condensed, purification wasperformed with a silica-gel column using chloroform and hexane as adeveloping solvent. After the purification, 32 g of the compound (c) wasobtained.

The analytical data of the compound (c) thus obtained is shown below.

ELEMENTAL ANALYSIS DATA C H S THEORETICAL VALUE (%) 29.7 4.2 66.1ANALYTICAL VALUE (%) 30.3 3.9 65.8 MS SPECTRUM   M⁺= 242 IR SPECTRUM  614 cm⁻¹; EPISULFIDE ¹³C-NMR SPECTRUM  1; 25.9 ppm 2; 33.3 ppm 3; 43.5ppm  4; 43.7 ppm 5; 45.7 ppm 6; 55.5 ppm

Synthesis Example 2 Synthesis of Compound (d)

After 250 g of 1-chloro-3-mercapto-2-propanol and 2.5 g of calciumhydroxide were mixed together in a reactor provided with a stirrer and athermometer, 190 g of epichlorohydrine was added dropwise to thesolution thus obtained which was maintained at a temperature of 40° C.Next, toluene and 350 g of a sodium hydroxide solution at aconcentration of 25% were added to the mixture thus obtained and werethen held for 3 hours for aging. After an organic layer obtained throughthe aging was washed with water twice, 120 g of thiourea, 5 g of aceticacid, and methanol were added thereto, and a mixture thus formed wasstirred for 10 hours at a temperature of 25° C. After aging, a toluenelayer was washed with an aqueous solution containing sodium chloride,thereby obtaining a toluene layer containing the compound (b). Next, 120g of thiourea, 5 g of acetic acid, and methanol were mixed with thistoluene layer thus obtained and were then stirred for 6 hours at atemperature of 25° C. After aging, the toluene layer thus obtained waswashed with an aqueous solution containing sodium chloride, therebyobtaining a toluene layer containing the compound (d). After the toluenelayer was condensed, purification was performed with a silica-gel columnusing chloroform and hexane as a developing solvent. After thepurification, 28 g of the compound (d) was obtained.

The analytical data of the compound (d) thus obtained is shown below.

ELEMENTAL ANALYSIS DATA C H S THEORETICAL VALUE (%) 34.2 4.8 61.0ANALYTICAL VALUE (%) 34.3 5.1 60.6 MS SPECTRUM   M⁺ = 210 IR SPECTRUM  614 cm⁻¹; EPISULFIDE ¹³C-NMR SPECTRUM  1; 25.5 ppm 2; 33.3 ppm 3; 33.6ppm  4; 36.3 ppm 5; 43.4 ppm 6; 53.2 ppm

Synthesis Example 3 Synthesis of Compound (e)

After 1,000 ml of methanol and 3.5 g of calcium hydroxide were chargedin a reactor provided with a stirrer and a thermometer, 450 g of ahydrogen sulfide gas was introduced thereinto for 6 hours while 555 g ofepichlorohydrine was added dropwise. In this step, the solution in thereactor was always maintained at a temperature of 0° C. to 5° C. Afterthe reaction was finished, the hydrogen sulfide gas was removed, and themethanol was then removed by distillation, thereby obtaining 760 g ofcrude 1-chloro-3-mercapto-2-propanol. The compound thus obtained wasprocessed by simple distillation, thereby obtaining a compound having apurity of 99%. Next, particles of solid iodine were added stepwise to amixture of 250 g of this distillated material, water, methanol, and 180g of sodium bicarbonate. Next, after toluene and 350 g of a sodiumhydroxide solution at a concentration of 25% were added, the mixturethus formed was held for 3 hours for aging. After an organic layerobtained through the aging was washed with water twice, 70 g ofthiourea, 5 g of acetic acid, and methanol were added thereto, and themixture thus formed was stirred for 8 hours at a temperature of 25° C.After aging, a toluene layer was washed with an aqueous solutioncontaining sodium chloride, thereby obtaining a toluene layer containingthe compound (e). After the toluene layer was condensed, purificationwas performed with a silica-gel column using chloroform and hexane as adeveloping solvent. After the purification, 25 g of the compound (e) wasobtained.

The analytical data of the compound (e) thus obtained is shown below.

ELEMENTAL ANALYSIS DATA C H O S THEORETICAL VALUE (%) 37.1 5.2 8.2 49.5ANALYTICAL VALUE (%) 37.8 4.8 7.5 49.9 MS SPECTRUM   M⁺ = 194 IRSPECTRUM   614 cm⁻¹; EPISULFIDE   840, 3055 cm⁻¹; EPOXIDE ¹³C-NMRSPECTRUM   1; 26.2 ppm 2; 34.6 ppm 3; 41.5 ppm   4; 45.7 ppm 5; 47.2 ppm6; 53.2 ppm

Synthesis Example 4 Synthesis of Compound (f)

After 250 g of 3-chloro-1-mercapto-2-propanol and 2.5 g of calciumhydroxide were mixed together in a reactor provided with a stirrer and athermometer, 190 g of epichlorohydrine was added dropwise to thesolution thus obtained which was maintained at a temperature of 40° C.Next, toluene and 350 g of a sodium hydroxide solution at aconcentration of 25% were added to the mixture thus obtained and werethen held for 3 hours for aging. After an organic layer obtained throughthe aging was washed with water twice, 70 g of thiourea, 5 g of aceticacid, and methanol were added thereto, and the mixture thus formed wasstirred for 6 hours at a temperature of 25° C. After aging, a toluenelayer was washed with an aqueous solution containing sodium chloride,thereby obtaining a toluene layer containing the compound (f). After thetoluene layer was condensed, purification was performed with asilica-gel column using chloroform and hexane as a developing solvent.After the purification, 24 g of the compound (f) was obtained.

The analytical data of the compound (f) thus obtained is shown below.

ELEMENTAL ANALYSIS DATA C H O S THEORETICAL VALUE (%) 44.4 6.2 9.9 39.5ANALYTICAL VALUE (%) 44.8 5.9 10.2 39.1 MS SPECTRUM   M⁺ = 162 IRSPECTRUM   615 cm⁻¹; EPISULFIDE   840, 3052 cm⁻1; EPOXIDE ¹³C-NMRSPECTRUM   1; 25.5 ppm 2; 33.6 ppm 3; 34.3 ppm   4; 46.3 ppm 5; 38.4 ppm6; 52.6 ppm

Thiourea in an amount of 152 g (1.05 equivalents) used as a thiationagent was allowed to react with epoxy groups of 178 g (purity of 95%) ofbis(2,3-epoxypropyl)disulfide in a solvent of 200 g of toluene and 100 gof methanol at 15° C. using 2.5 g (0.022 equivalents) of acetic acid asa catalyst. After the reaction was completed, an organic layer waswashed three times by adding an aqueous solution containing sodiumchloride and was then recovered, followed by condensation. The residuethus obtained was dissolved in cyclohexane, and the supernatant thereofwas passed through a silica gel column for condensation. The resultantresidue thus obtained was a polymerizable composition in which thecompound (a) was contained, and the total of the compound (c) and thecompound (e) was 0.8 mass percent. After this polymerizable compound waspassed through a silica gel column for chromatographic purificationusing chloroform and hexane as a developing solvent, the total of thecompound (c) and the compound (e) in the resultant polymerizablecomposition was 0 mass percent. To 100 g of this resultant compositionobtained by the chromatographic purification, 0.1 g ofN,N-dimethylcyclohexylamine was added as a curing catalyst, followed bystirring, and after defoamed under vacuum for 0.1 hours, the resultantcomposition was cast in a molding tool formed of a glass mold and agasket. This mold was gradually heated from 30° C. to 120° C., andpolymerization was performed for 24 hours. After this polymerization,the mold was gradually cooled, and the resin was then recovered from themold. The properties of the resultant resin are shown in Table-1. Theresultant resin was superior having a YI of 5.4 and no optical strain.

Example 2

Synthesis was performed in a manner equivalent to that in Example 1, inwhich thiourea in an amount of 1.05 equivalents was used as a thiationagent with respect to one epoxy group of bis(2,3-epoxypropyl)disulfide.In the resultant polymerizable composition, the compound (a) wascontained, and in addition, the total of the compound (c) and thecompound (e) was 0.8 mass percent. Without performing chromatographicpurification, 0.1 g of N,N-dimethylcyclohexylamine was added as a curingcatalyst to 100 g of this resultant composition, followed by stirring,and after defoamed under vacuum for 0.1 hours, the resultant compositionwas cast in a molding tool formed of a glass mold and a gasket. Thismold was gradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin was superior having no optical strain.

Example 3

Operation similar to that in Example 2 was performed 10 times for yieldevaluation. The total of the compound (c) and the compound (e) in eachof the resultant polymerizable compositions was stable and was 1 masspercent or less. The refractive indexes and the hues of the resinsobtained by polymerization were the same as those obtained in Example 1,the optical strain was also not observed, and hence the resultant resinswere superior.

Example 4

In a manner equivalent to that in Example 0.1, reaction was performedexcept that thiourea in an amount of 1.15 equivalents was used withrespect to one epoxy group, and a polymerizable composition wasobtained. In the resultant polymerizable composition, the compound (a)was contained, and in addition, the total of the compound (c) and thecompound (e) was 0.7 mass percent. Next, 0.1 g ofN,N-dimethylcyclohexylamine was added as a curing catalyst to 100 g ofthis polymerizable composition, followed by stirring, and after defoamedunder vacuum for 0.1 hours, the resultant composition was cast in amolding tool formed of a glass mold and a gasket. This mold wasgradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin was superior having no optical strain.

Example 5

Operation similar to that in Example 4 was performed 10 times for yieldevaluation. The total of the compound (c) and the compound (e) in eachof the resultant polymerizable compositions was stable and was 1 masspercent or less. The refractive indexes and the hues of the resinsobtained by polymerization were the same as those obtained in Example 1,the optical strain was also not observed, and hence the resultant resinswere superior.

Example 6

As an epoxy compound, bis(2,3-epoxypropyl)sulfide was used, and in amanner equivalent to that in Example 1, reaction and purification usinga column chromatographic method were performed. The total of thecompound (d) and the compound (f) in the resultant polymerizablecomposition obtained after purification was 0 mass percent. Next, 0.1 gof N,N-dimethylcyclohexylamine was added as a curing catalyst to 100 gof this polymerizable composition, followed by stirring, and afterdefoamed under vacuum for 0.1 hours, the resultant composition was castin a molding tool formed of a glass mold and a gasket. This mold wasgradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin was superior having a YI of 4.2 and no optical strain.

Example 7

In a manner equivalent to that in Example 6, reaction was performedexcept that a thiation agent in an amount of 1.15 equivalents was usedwith respect to one epoxy group and that the reaction temperature wasset to 25° C. In the resultant polymerizable composition thus obtained,the compound (b) was contained, and in addition, the total of thecompound (d) and the compound (f) was 0.9 mass percent. Next, 0.1 g ofN,N-dimethylcyclohexylamine was added as a curing catalyst to 100 g ofthis polymerizable composition, followed by stirring, and after defoamedunder vacuum for 0.1 hours, the resultant composition was cast in amolding tool formed of a glass mold and a gasket. This mold wasgradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin was superior having no optical strain.

Example 8

Operation similar to that in Example 7 was performed 10 times for yieldevaluation. The total of the compound (d) and the compound (f) in eachof the resultant polymerizable compositions was stable and was 1.5 masspercent or less. The refractive indexes and the hues of the resinsobtained by polymerization were the same as those obtained in Example 6,the optical strain was also not observed, and hence the resultant resinswere superior.

Example 9

In a manner equivalent to that in Example 6, reaction was performedexcept that a thiation agent in an amount of 1.20 equivalents was usedwith respect to one epoxy group. In the resultant polymerizablecomposition, the compound (b) was contained, and in addition the totalof the compound (d) and the compound (f) was 1.2 mass percent. Next, 0.1g of N,N-dimethylcyclohexylamine was added as a curing catalyst to 100 gof this polymerizable composition, followed by stirring, and afterdefoamed under vacuum for 0.1 hours, the resultant composition was castin a molding tool formed of a glass mold and a gasket. This mold wasgradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin was superior having no optical strain.

Example 10

Operation similar to that in Example 9 was performed 10 times for yieldevaluation. The total of the compound (d) and the compound (f) in eachof the resultant polymerizable compositions was stable and was 1.5 masspercent or less. The refractive indexes and the hues of the resinsobtained by polymerization were the same as those obtained in Example 6,the optical strain was also not observed, and hence the resultant resinswere superior.

Example 11

In a manner equivalent to that in Example 4, reaction was performedexcept that a thiation agent in an amount of 1.28 equivalents was usedwith respect to one epoxy group and that the reaction temperature wasset to 35° C. In the resultant polymerizable composition, the compound(b) was contained, and in addition, the total content of the compound(d) and the compound (f) was 1.4 mass percent. Next, 0.1 g ofN,N-dimethylcyclohexylamine was added as a curing catalyst to 100 g ofthis polymerizable composition, followed by stirring, and after defoamedunder vacuum for 0.1 hours, the resultant composition was cast in amolding tool formed of a glass mold and a gasket. This mold wasgradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin was superior having no optical strain.

Example 12

Operation similar to that in Example 11 was performed 10 times for yieldevaluation. The total of the compound (d) and the compound (f) in eachof the resultant polymerizable compositions was stable and was 1.5 masspercent or less. The refractive indexes and the hues of the resinsobtained by polymerization were the same as those obtained in Example 6,the optical strain was also not observed, and hence the resultant resinswere superior.

Example 13

In a manner equivalent to that in Example 6, reaction was performedexcept that a thiation agent in an amount of 1.28 equivalents was usedwith respect to one epoxy group, that the reaction temperature was setto 35° C., and that a composition containing a polyepoxy compound wasadded dropwise to a composition containing the thiation agent. In theresultant polymerizable composition, the compound (b) was contained, andthe total content of the compound (d) and the compound (f) was 1.2 masspercent. Next, 0.1 g of N,N-dimethylcyclohexylamine was added as acuring catalyst to 100 g of this polymerizable composition, followed bystirring, and after defoamed under vacuum for 0.1 hours, the resultantcomposition was cast in a molding tool formed of a glass mold and agasket. This mold was gradually heated from 30° C. to 120° C., andpolymerization was performed for 24 hours. After this polymerization,the mold was gradually cooled, and the resin was then recovered from themold. The properties of the resultant resin are shown in Table-1. Theresultant resin was superior having no optical strain.

Example 14

Operation similar to that in Example 13 was performed 10 times for yieldevaluation. The total of the compound (d) and the compound (f) in eachof the resultant polymerizable compositions was stable and was 1.5 masspercent or less. The refractive indexes and the hues of the resinsobtained by polymerization were the same as those obtained in Example 6,the optical strain was also not observed, and hence the resultant resinswere superior.

Comparative Example 1

In a manner equivalent to that in Example 1, reaction was performedexcept that a thiation agent in an amount of 3.5 equivalents was usedwith respect to one epoxy group. In the resultant polymerizablecomposition, the compound (a) was contained, and in addition, the totalof the compound (c) and the compound (e) was 4.2 mass percent. Thispolymerizable composition had a strong yellow hue which could be easilyobserved by visual inspection. Next, 0.1 g ofN,N-dimethylcyclohexylamine was added as a curing catalyst to 100 g ofthis polymerizable composition, followed by stirring, and after defoamedunder vacuum for 0.1 hours, the resultant composition was cast in amolding tool formed of a glass mold and a gasket. This mold wasgradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin had a high YI value and also had optical strain, and therefractive index thereof was different from that in Example 1.

Comparative Example 2

Operation similar to that in Comparative Example 2 was performed 10times for yield evaluation. The total of the compound (c) and thecompound (e) in each of the resultant polymerizable compositions was 4mass percent or more. As for the refractive indexes and the hues of theresins obtained by polymerization, the YI value was high and therefractive index was different as compared to those in Example 1.Furthermore, eight resins out of the 10 resins had optical strain, andhence decrease in yield was also confirmed.

Comparative Example 3

In a manner equivalent to that in Example 6, reaction was performedexcept that a thiation agent in an amount of 0.8 equivalents was usedwith respect to one epoxy group. In the resultant polymerizablecomposition, the compound (b) was contained, and in addition, the totalcontent of the compound (d) and the compound (f) was 5.6 mass percent.Next, 0.1 g of N,N-dimethylcyclohexylamine was added as a curingcatalyst to 100 g of this polymerizable composition, followed bystirring, and after defoamed under vacuum for 0.1 hours, the resultantcomposition was cast in a molding tool formed of a glass mold and agasket. This mold was gradually heated from 30° C. to 120° C., andpolymerization was performed for 24 hours. After this polymerization,the mold was gradually cooled, and the resin was then recovered from themold. The properties of the resultant resin are shown in Table-1. Theresultant resin had a high YI value and also had optical strain, and therefractive index thereof was different from that in Example 6.

Comparative Example 4

Operation similar to that in Comparative Example 3 was performed 10times for yield evaluation. The total of the compound (d) and thecompound (f) in each of the resultant polymerizable compositions was 4mass percent or more. As for the refractive indexes and the hues of theresins obtained by polymerization, the YI value was high and therefractive index was different as compared to those in Example 1.Furthermore, all ten resins thus formed had optical strain, and hencedecrease in yield was also confirmed.

Comparative Example 5

In a manner equivalent to that in Example 4, reaction was performedexcept that a thiation agent in an amount of 3.5 equivalents was usedwith respect to one epoxy group, and that the reaction temperature wasset to 60° C. In the resultant polymerizable composition, the compound(b) was contained, and in addition, the total content of the compound(d) and the compound (f) was 5.2 mass percent. Next, 0.1 g ofN,N-dimethylcyclohexylamine was added as a curing catalyst to 100 g ofthis polymerizable composition, followed by stirring, and after defoamedunder vacuum for 0.1 hours, the resultant composition was cast in amolding tool formed of a glass mold and a gasket. This mold wasgradually heated from 30° C. to 120° C., and polymerization wasperformed for 24 hours. After this polymerization, the mold wasgradually cooled, and the resin was then recovered from the mold. Theproperties of the resultant resin are shown in Table-1. The resultantresin had a high YI value and also had optical strain, and therefractive index thereof was different from that in Example 4.

Comparative Example 6

Operation similar to that in Comparative Example 5 was performed 10times for yield evaluation. The total of the compound (d) and thecompound (f) in each of the resultant polymerizable compositions was 4mass percent or more. As for the refractive indexes and the hues of theresins obtained by polymerization, the YI value was high and therefractive index was different as compared to those in Example 6.Furthermore, eight resins out of the 10 resins had optical strain, andhence decrease in yield was also confirmed.

TABLE 1 Refrac- tive Index Optical Polymerizable Composition ne HueStrain Example 1 0 mass percent of compounds 1.744 Blank ∘ (c) and (e)contained in (good) polymerizable composition Example 2 0.8 mass percentofcompounds 1.744 ∘ ∘ (c) and (e) contained in (good) (good)polymerizable composition Example 4 0.7 mass percent of compounds 1.744∘ ∘ (c) and (e) contained in (good) (good) polymerizable compositionExample 6 0 mass percent of compounds 1.705 Blank ∘ (d) and (f)contained in (good) polymerizable composition Example 7 0.9 mass percentof compounds 1.705 ∘ ∘ (d) and (f) contained in (good) (good)polymerizable composition Example 9 1.2 mass percent of compounds 1.705∘ ∘ (d) and (f) contained in (good) (good) polymerizable compositionExam- 1.4 mass percent of compounds 1.705 ∘ ∘ ple 11 (d) and (f)contained in (good) (good) polymerizable composition Exam- 1.2 masspercent of compounds 1.705 ∘ ∘ ple 13 (d) and (f) contained in (good)(good) polymerizable composition Compara- 4.2 mass percent of compounds1.747 x x tive (c) and (e) contained in (not (not Example 1polymerizable composition good) good) Compara- 5.6 mass percent ofcompounds 1.702 x x tive (d) and (f) contained in (not (not Example 3polymerizable composition good) good) Compara- 5.2 mass percent ofcompounds 1.708 x x tive (d) and (f) contained in (not (not Example 5polymerizable composition good) good)

INDUSTRIAL APPLICABILITY

According to the present invention, a transparent cured resin used as anoptical material in the field of ultra high refractive index applicationcan be obtained in which variation in refractive index and variation inoptical strain are suppressed, and as a result, in the field of glasslenses, the yield of lenses can be improved.

1. A method for manufacturing a polymerizable composition comprising acompound which has at least one structure represented by formula (1),comprising forming a polythioepoxy compound from a polyepoxy compound,wherein a thiation agent in an amount of 0.9 to 1.3 equivalents is usedwith respect to one epoxy equivalent of the polyepoxy compound so thatthe total of a thioepoxy compound A which has at least one structurerepresented by formula (2) and at least one structure represented byformula (3), and a thioepoxy compound B which has at least one structurerepresented by formula (4) and at least one structure represented byformula (3), which are in the polymerizable composition, is 4 masspercent or less with respect to the total mass of the polymerizablecomposition, wherein formulae (1) to (4) are as follows:

(where R₁ represents a hydrocarbon having 1 to 10 carbon atoms, R₂, R₃,and R₄ each represent a hydrocarbon group having 1 to 10 carbon atoms ora hydrogen atom)


2. The manufacturing method according to claim 1, wherein the thioepoxycompound A is a compound represented by formula (5), the thioepoxycompound B is a compound represented by formula (6), and a compoundhaving at least one structure represented by formula (1) is representedby formula (7):

(where Y represents a substituted or unsubstituted, linear, branched, orcyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,a substituted or unsubstituted 1,4-dithiane group, an arylene group, oran aralkylene group, m represents an integer of 0 to 2, and n representsan integer of 0 to 4)

(where R₅ to R₁₀ each represent a hydrocarbon group having 1 to 10carbon atoms or hydrogen, Y represents a substituted or unsubstituted,linear, branched, or cyclic divalent hydrocarbon group having 1 to 10carbon atoms, a substituted or unsubstituted 1,4-dithiane group, anarylene group, or an aralkylene group, m represents an integer of 0 to2, and n represents an integer of 0 to 4).
 3. The manufacturing methodaccording to claim 2, wherein the thioepoxy compound A comprises2,3-epidithiopropyl(2,3-epithiopropyl)disulfide and/or2,3-epidithiopropyl(2,3-epithiopropyl)sulfide, the thioepoxy compound Bcomprises 2,3-epoxypropyl(2,3-epithiopropyl)disulfide and/or2,3-epoxypropyl(2,3-epithiopropyl)sulfide, and the compound representedby formula (7) comprises bis(2,3-epithiopropyl)disulfide and/orbis(2,3-epithiopropyl)sulfide.
 4. A method for manufacturing apolymerizable composition comprising a compound which has at least onestructure represented by formula (1), comprising forming a polythioepoxycompound from a polyepoxy compound, wherein a thiation agent in anamount of 0.9 to 1.3 equivalents is used with respect to one epoxyequivalent of the polyepoxy compound, and the reaction temperature isset to 0° C. to 50° C. so that the total of a thioepoxy compound A whichhas at least one structure represented by formula (2) and at least onestructure represented by formula (3), and a thioepoxy compound B whichhas at least one structure represented by formula (4) and at least onestructure represented by formula (3), which are in the polymerizablecomposition, is 4 mass percent or less with respect to the total mass ofthe polymerizable composition, wherein formulae (1) to (4) are asfollows:

(where R₁ represents a hydrocarbon having 1 to 10 carbon atoms, R₂, R₃,and R₄ each represent a hydrocarbon group having 1 to 10 carbon atoms ora hydrogen atom)


5. The manufacturing method according to claim 4, wherein the thioepoxycompound A is a compound represented by formula (5), the thioepoxycompound B is a compound represented by formula (6), and a compoundhaving at least one structure represented by formula (1) is representedby formula (7):

(where Y represents a substituted or unsubstituted, linear, branched, orcyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,a substituted or unsubstituted 1,4-dithiane group, an arylene group, oran aralkylene group, m represents an integer of 0 to 2, and n representsan integer of 0 to 4)

(where R₅ to R₁₀ each represent a hydrocarbon group having 1 to 10carbon atoms or hydrogen, Y represents a substituted or unsubstituted,linear, branched, or cyclic divalent hydrocarbon group having 1 to 10carbon atoms, a substituted or unsubstituted 1,4-dithiane group, anarylene group, or an aralkylene group, m represents an integer of 0 to2, and n represents an integer of 0 to 4).
 6. The manufacturing methodaccording to claim 5, wherein the thioepoxy compound A comprises2,3-epidithiopropyl(2,3-epithiopropyl)disulfide and/or2,3-epidithiopropyl(2,3-epithiopropyl)sulfide, the thioepoxy compound Bcomprises 2,3-epoxypropyl(2,3-epithiopropyl)disulfide and/or2,3-epoxypropyl(2,3-epithiopropyl)sulfide, and the compound representedby formula (7) comprises bis(2,3-epithiopropyl)disulfide and/orbis(2,3-epithiopropyl)sulfide.
 7. A method for manufacturing apolymerizable composition comprising a compound which has at least onestructure represented by formula (1), comprising forming a polythioepoxycompound from a polyepoxy compound, wherein a thiation agent in anamount of 0.9 to 1.3 equivalents is used with respect to one epoxyequivalent of the polyepoxy compound, an acid or its anhydride in anamount of 0.2 equivalents or less is used with respect to one epoxyequivalent of the polyepoxy compound, and the reaction temperature isset to 0° C. to 50° C. so that the total of a thioepoxy compound A whichhas at least one structure represented by formula (2) and at least onestructure represented by formula (3), and a thioepoxy compound B whichhas at least one structure represented by formula (4) and at least onestructure represented by formula (3), which are in the polymerizablecomposition, is 4 mass percent or less with respect to the total mass ofthe polymerizable composition, wherein formulae (1) to (4) are asfollows:

(where R₁ represents a hydrocarbon having 1 to 10 carbon atoms, R₂, R₃,and R₄ each represent a hydrocarbon group having 1 to 10 carbon atoms ora hydrogen atom)


8. The manufacturing method according to claim 7, wherein the thioepoxycompound A is a compound represented by formula (5), the thioepoxycompound B is a compound represented by formula (6), and a compoundhaving at least one structure represented by formula (1) is representedby formula (7):

(where Y represents a substituted or unsubstituted, linear, branched, orcyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms,a substituted or unsubstituted 1,4-dithiane group, an arylene group, oran aralkylene group, m represents an integer of 0 to 2, and n representsan integer of 0 to 4)

(where R₅ to R₁₀ each represent a hydrocarbon group having 1 to 10carbon atoms or hydrogen, Y represents a substituted or unsubstituted,linear, branched, or cyclic divalent hydrocarbon group having 1 to 10carbon atoms, a substituted or unsubstituted 1,4-dithiane group, anarylene group, or an aralkylene group, m represents an integer of 0 to2, and n represents an integer of 0 to 4).
 9. The manufacturing methodaccording to claim 8, wherein the thioepoxy compound A comprises2,3-epidithiopropyl(2,3-epithiopropyl)disulfide and/or2,3-epidithiopropyl(2,3-epithiopropyl)sulfide, the thioepoxy compound Bcomprises 2,3-epoxypropyl(2,3-epithiopropyl)disulfide and/or2,3-epoxypropyl(2,3-epithiopropyl)sulfide, and the compound representedby formula (7) comprises bis(2,3-epithiopropyl)disulfide and/orbis(2,3-epithiopropyl)sulfide.